Multifunctional initiators

ABSTRACT

MULTIFUNCTIONAL INITIATORS ARE PREPARED BY CONTACTING ORGANOMONOLITHIUM COMPOUNDS WITH SELECTED COMPOUNDS CONTAINING AT LEAST TWO CARBON-CARBON DOUBLE BONDS IN THE PRESENCE OF POLAR COMPOUNDS.

States Patent 01 se 3,734,972 Patented May 22, 1973 US. Cl. 260-665 R *5 Claims ABSTRACT OF THE DISCLOSURE Multifunctional initiators are prepared by contacting organomonolithium compounds with selected compounds containing at least two carbon-carbon double bonds in the presence of polar compounds. i

This application is a continuation-in-part of United States application Ser. No. 800,271, filed Feb. 18, 1969, now abandoned.

This invention relates to an improved multifunctional polymerization initiator. In another aspect, it relates to an improved process for polymerizing conjugated dienes and monovinyl-substituted aromatic compounds. In still another aspect, it relates to a process for polymerizing conjugated dienes to form polymers containing a high degree of cis-1,4-addition.

It has now been discovered that an excellent multifunctional initiator can be produced by contacting an organomonolithium compound with selected compounds containing at least two carbon-carbon double bonds selected from aliphatic hydrocarbons, alicyclic hydrocarbons, or tertiary nitrogen-containing heterocyclic compounds, in the presence of a polar compound selected from alkali metal alkoxides, secondary and tertiary amines, or hexaalkylphosphoramides.

It is an object of this invention to provide a multifunctional lithium based initiator which is effective in the preparation of block copolymers having high green tensile strength and elongation properties. Another object of this invention is to provide a polymerization 'process wherein homopolymers of conjugated dienes can be prepared which contain a high degree of cisl,4-addition. Other objects, advantages, and features of our invention will be apparent to those skilled in the art from the following discussion and examples herein set forth.

According to the present invention, multifunctional initiators containing at least two carbon-lithium bonds are readily prepared. They are branched and the branches are terminated with lithium substituents which serve as reaction sites for polymerization initiation. Branched polymers result when polymerizations are initiated in the presence of these multifunctional polymerization initiators. Multifunctional lithium initiators can be prepared according to this invention which are soluble or insoluble in the hydrocarbon'reaction medium depending on the molar ratio of organolithium compound per carboncarbon double bond in the selected compound containing two or more carbon-carbon double bonds, and depending on the type of reactant containing the at least two carboncarbon double bonds. Insolubility is a feature that can be an advantage in that the insoluble compounds can be essentially freed of diluent, added polar'material, soluble unreacted organomonolithiu'm and soluble reactant. This advantage can be more fully appreciated when one considers that polar compounds are known to decrease 1,4-addition in'the polymerization of conjugated diene by various organometallic initiators including organolithium.

, The organomonolithium compounds suitable for employment according to this invention can be represented by the general formula RLi wherein R is an alkyl, cycloalkyl, aryl, cycloalkenyl, or alkenyl radical, or combinations thereof, such as aralkyl alkaryl, alkenylcycloalkyl; containing from 1 to 12 carbon atoms per molecule. Exemplary organomonolithium compounds are methyllithium; n-butyllithium; secondary-butyllithium; tertiary butyllithium; cyclohexyllithium; 4 tolyllithium; phenyllithium; 3 phenyl 1 hexyllithium; 1 lithio-4- dodecene; and 4-lithiocyclooctene. I

The selected compounds containing two or more carbon-carbon double bonds employed according to this invention can be selected from (a) aliphatic hydrocarbons, (b) alicyclic hydrocarbons, and (c) tertiary nitrogencontaining heterocyclic compounds in which said nitrogen is bound to three different carbon atoms.

The aliphatic hydrocarbons (a) can contain from ,3 to carbon atoms per molecule and can be represented by the general formula wherein each R can be hydrogen, an alkyl cycloalkyl,

1 alkenyl or cycloalkenyl radical, and combination thereof, containing from 1 to 27 carbon atoms, with the restriction that at least one R is an unsaturated radical.

The alicyclic hydrocarbons (b) can contain from 5 to 30 carbon atoms per molecule and comprise monocyclic or polycyclic conjugated or nonconjugated dienes or higher polyenes.

The tertiary nitrogen-containing heterocyclic compounds (0) can contain from 4 to 30 carbon atoms per molecule, from 1 to 3 of said tertiary nitrogen atoms per molecule, and can be a monocyclic or polycyclic diene or higher polyene. In the alicyclic hydrocarbon compounds (b) and the tertiary nitrogen-containing heterocyclic compounds (c), the carbon-carbon unsaturation can also be exocyclic.

Exemplary of compounds representing the aliphatic hydrocarbons (a) are 1,3-butadiene, isoprene, piperylene, 2,3-dirnethyl-1,3-butadiene; 2,5-dimethyl-1,5 hexadiene; 1,5-heXadiene; 2,6-dimethyl-2,7-octadiene; 2,5 -dimethyl- 2,4 haxadiene; 2,6,10 dodecatriene, 1,2 bis(3 cyclohexen-1-yl)-ethylene; and l,3,5,7,9-triacontapentaene.

Exemplary of the alicyclic hydrocarbons (b) are cyclopentadiene; 1,4 cyclohexadiene; 4 vinylcyclohexene; 1, 2,4 'trivinylcyclohexane; 1,5 cyclooctadiene; l,3,5,7- cyclooctatetraene; 1,5,9 cyclododecatriene; bicyclo-[2,2, 1] hepta-2,5 diene; bicyclo [2,2,2] octa 1 2,5,7- triene; 1,2,5,6,9,10-hexapropyl-l,5,9 cyclododecatriene; and tricyclo-[5,3,2,0 ]dodeca-2,5,1l-triene.

Exemplaryof the tertiary nitrogen-containing heterocyclic compounds (c) are l-rnethylpyrrole; 1 vinylpyr role; l-methyl 3 vinylpyrrole; l-ethyl 3,5 divinylpiperidine; 1,4-diethyl-2,6 divinylpiperazine; 3,5,8 trivinylquinuclidine; l-butyl-6-vinyl 1,2,3,6 tetrahydropyridine; 1,3,5-trihexyl-2,4,6-trivinyl 1,3,5 triazacyclohexene; and 1,2,l0-triheptyl-2H-azecine.

The polar compounds that can be employed according to this invention are (l) alkali metal alkoxides, (2) secondary amines, (3) tertiary amines, or (4) hexaalkylphosphoramides.

Exemplary alkali metal alkoxides that can be employed are the lithium, sodium, potassium, rubidium, or cesium salts of alcohols such as methyl alcohol, ethyl alcohol, tertiary-butyl' alcohol, eicosyl alcohol, phenol, Z-naphthol, and the like. The alkali metal alkoxides can contain from 1 to 20 carbon atoms per molecule. Presently preferred 5 are the potassium salts.

3 The secondary amines can be represented by the general formula ltN-II wherein each R can be an alkyl, cycloalkyl, aryl radical, or combination thereof such as aralkyl, and the like. Which radicals together with the N can form a saturated heterocyclic ring contacting from 4 to 7 carbon atoms, wherein said R radicals contain from 1 to 20 carbon atoms. Exemplary secondary amines are di-n-butylamine; -N-methyl-N-eiscosylamine; diethylamine; diphenylamine;

V soluble multifunctional initiators is from 0.75 to 1.25 per N-methyl aniline; piperidine; Z-methyl-l-azacyclooctane;

and, the like.

The tertiary amines that can be employed according to this invention can be represented by the general formula wherein each R" can be an alkyl, cycloalkyl, or aryl .radical, or. combinations thereof such as aralkyl and the like, which radicals together with the N can form a saturated heterocyclic ring containing from 4 to 7 carbon atoms, and wherein said R" radicals contain from 1 to 20 carbon atoms. Exemplary tertiary amines are trimethylamine; triethylamine; tricyclohexylamine; trioctylamine; trieicosylamine; triphenylamine; N-ethyl-N-cyclohexyl-N- phenylamine; and the like.

The hexaalkylphosphoramides can be represented by the general formula wherein each R can be an alkyl radical containing from 1 to 8 carbon atoms. Exemplary of such compounds are hexamethylphosphoramide and hexaoctylphosphoramide.

The organomonolithium compound is contacted with the compound containing at least two carbon-carbon double bonds in the presence of said polar compounds. This reaction can be performed in the presence or absence of an inert hydrocarbon diluent. Suitable diluents include aliphatic, cycloaliphatic, and aromatic hydrocarbons, or mixtures of such hydrocarbons. The preferred diluents are the aliphatic and cycloaliphatic hydrocarbons containing from 4 to 10 carbon atoms per molecule. Exemplary of suitable diluents are butane, pentane, hexane. 2 methylbutane, heptane, decane cyclohexane, 1,2 dimethylcyclooctane, benzene, and toluene. The amount of diluent, if employed, can vary over abroad range andcan be conveniently described in terms of the molar concentration of the organomonolithium compound in the diluent. This concentration can vary from about 0.1 M to that obtained in the absence of diluent while the preferred range is from 1 M to 4 M.

The amount of said polar compound employed in the reaction with the organomonolithium compound and the compound containing at least 2 carbon-carbon double bonds can vary over a wide range. The molar ratio of said polar compound to said compound containing at least 2 carbon-carbon double bonds is generally in the range of from 0.00l:1 to 10:1 while the preferred range is from 0.5:1 to 2:1.

The molar ratio of organomonolithium compound to N-methylazacyclooctane; l-ethylpiperidine;

said compounds containing at least 2 carbon-carbon each carbon-carbon double bond in one mole of said comp d. Th p se y p ferred ratio for y qca bcu ineach carbon-carbon double bond in one mole of said compound.

'In the case where the reactant containing two or more carbon-carbon double bonds is selected from among the defined class of alicyclic hydrocarbons or the defined class of tertiary nitrogen-containing heterocyclic compounds, then hydrocarbon insoluble multifunctional initiators are produced, as is also the case of the aliphatic hydrocarbons other than conjugated dienes.

In the case where the reactant containing two or more carbon-carbon double bonds is selected from among the class of aliphatic hydrocarbons which are also polymerizable conjugated dienes, then the ratio of organomonolithium compound per each carbon-carbon double bond in one moleof the reactant should be below about 0.5, preferably below about 0.33, to prepare hydrocarbon soluble multifunctional initiators. Conversely, the ratio, in

the case of these particular classes of reactants, should be about 0.5 or above to produce hydrocarbon insoluble multifunctional initiators.

Furthermore, when the reactant containing two or more carbon double bonds is selected from the aforesaid classes of aliphatic hydrocarbons or alicyclic hydrocarbons, and the polar compound is chosen from among the class of alkali metal alkoxides, such as potassium alkoxide, and hydrocarbon soluble multifunctional initiators are desired, then a molar ratio of organomonolithium compoundzalkali metal alkoxide of at least about 1:1 should be employed.

The temperature employed in this reaction can vary from about 0 to 150 C. The preferred range is from 30 to C. The pressure can also vary over a wide range, although it is preferred that the pressure be sufficient to maintain the reaction mixture in a predominantly liquid form.

The time employed in the reaction of said organomonolithium compound and said containing at least 2 carbon-carbon double bonds in the presence of said polar compound can vary over a broad range and will, in general, depend upon the temperature, concentration of reactants, and the reactivity of the chosen reactants. The range of time employed can be from about 10 seconds to 72 hours, while the preferred range is from about 0.25 to 6 hours.

As hereinbefore stated, when the multilithium initiators are prepared according to this invention so as to be generally insoluble in the reaction medium, their insolubility enables these compounds to be essentially freed of diluent, added polar material, soluble unreacted organomonolithium, and soluble reactant, i.e., the compound containing at least 2 carbon-carbon double bonds. It should be noted that if a polymer is desired which contains 2- or more terminal reactant groups, derived from terminal carbon-lithium groups, the presence of unreacted organomonolithium in the multilithium initiator product generally would not be desirable. Nevertheless, the multilithium initiators of this invention can be employed without separation from the reaction mixture if the above observations have no relevance to the particular multilithium initiator and the polymerization system of choice.

The hydrocarbon insoluble multifunctional initiators of this invention can be separated from the reaction mixtures by any convenient method. Methods generally known to the art such as decantation of the liquid phase and washing the solid initiator one or more times with fresh portions .of inert diluent; evaporation of the liquid phase under heat and reduced pressure followed by washing as above; filtering of the reaction mixture and washing the solidas above on the filter; and centrifuging the reaction mixture, decanting the liquid phase, and washing the solid phaseby agitation withheated diluent and repeating the centrifuging step, are methods that can be employed. These separation steps should be carried out with the exc usion of ai and moisture. The s pa ated, washed solid initiator then is generally dispersed in an inert diluent for convenience in handling. The amount of lithium in the initiator can be conveniently determined by titration of a knovtm volume of the dispersion with standardized hydrochloric acid employing phenolphthalein indicator to determine the end point of titration.

The hydrocarbon soluble multilithium initiators pro- .Vide desirable ease in handling, forming stable solutions that can be stored forlong intervals after preparation.

The multifunctional initiators of this invention can be employed for the polymerization of conjugated dienes, and mixtures thereof, containing from 4 to 12 carbon atoms per molecule. Vinyl-substituted aromatic compounds, and mixtures thereof, containing 8 to 24 carbon atoms per molecule and mixtures of said conjugated dienes, or mixtures thereof, with said vinyl-substituted aromatic compounds, or mixtures thereof, can also be polymerized. Vinyl-substituted heterocyclic nitrogen compounds can also be employed. The mixtures of conjugated dienes and vinyl-substituted aromatic compounds can be employed in any ratio desired. These mixtures of conjugated dienes and vinyl-substituted aromatic compounds can be polymerized by contacting the entire mixture with the initiators of this invention or each of the separate monomer mixture components can be added and polymerized essentially to completion prior to the addition of the subsequent monomer. Any desired sequence of additioncan beemployed in the latter procedure. Ex emplary monomers thatcan be employed according to this invention .are, 1,3-butadiene; 2-methyl-l,3-butadiene; 2-phenyl-l,3-butadiene; 2 methyl 1 1,3 pentadiene; 1,3- pentadiene; 1,3-dodecadiene; styrene; l-vinylnaphthalene; 2-vinylnaphthalene; 4-methylstyrene; and 4-vinylpyridine.

The polymerization process usin the initiators of this invention can be conducted in the presence of added polar compounds such as amines, ethers, thioethers, and the like. The amount of polar compound employed can vary over a wide range but will generally be in the range of 0.01 to 100 parts of polar compound per 100 parts of monomers employed. When employing the hydrocarbon soluble multilithium initiators of this invention, it is often not necessary to add additional polar compound since the amount of polar compound employed in the initiator preparation will be sufficient for the purposes at hand.

It is preferred that the polymerization process be conducted in the presence of a suitable diluent such as benzene, toluene,. xylene; cyclohexane, methylcyclohexane, n-butane, n-hexane, n-heptane, isooctane, mixtures of these and the like. Generally, the diluent is selected from inert hydrocarbons, i.e., parafiins, cycloparaftins, and aromatics containing from 4 to carbon atoms per molecule.

Polymerization conditions generally known to the art can be suitably employed. Polymerization temperatures can vary over abroad range and are generally from about '100 to 300 F. It is preferred to operate at a temperature of at least 85- F. The initiator concentration employed is in the range of about 0.25 to 200 milliequivalents of lithium per 100 grams of monomer, preferably about 1 to 100. .Thdmilliequivalentsof lithium can be conveniently de: termined by an alkalinity titration of a known volume of the reaction mixture containing the multifunctional initiatorvSaid alkalinity titration employs standardized acid; e.g., HCl, and an indicator such as phenolphthalein to detcrmine the endpoint of titration. The alkaline normality thus obtained provides a value for the milliequivalents of lithium per milliliter of reaction mixture containing the multifunctional initiator. The alkalinity concentration (normality) thus determined then is employed for charginga known. quantity of milliequivalents of lithium in polymerization recipes employing the multifunctional initiators of this invention.

As hereinbefore stated, polymers made with the initiators of this invention contain 2 or more terminal lithium atoms..Thus, these polymers can be reacted with known reagents by known processes by which polymers with a wide variety of end groups can be prepared. Exemplary of such end groups are halogen and the like, wherein R' can be hydrogen, or an aliphatic, cycloaliphatic or aromtaic radical, or combination thereof such as cycloalkylaryls and the like. These polymers then are suitable for reaction with polyfunctionalreagents to effect a coupling and/or curing reaction. Also, these polymers can be reacted with other polymers having like or unlike reactive end groups to elfect a coupling and/or curing reaction. Depending upon their particular properties, the polymers of this invention find wide application in the preparation of molded articles, such as tires and other rubber articles. In some instances, they can be extruded, calendered, and otherwise treated as conventional plastics.

It should be noted that another advantage is realized when employing initiators of this invention. Block copolymers of the type S B S can be prepared wherein B is a segment of conjugated diene homopolymer and S is a segment of vinyl-substituted aromatic compound homopolymer. These and similar products find application in the preparation of rubber articles often without the use of curing agents. Homopolymers of conjugated dienes can also be prepared with the hydrocarbon insoluble multilithium initiators which contain a high degree of cis-1,4-addition which are easily processed and have a reduced tendency to coldflow.

Illustrative of the foregoing discussion and not to be interpreted as a limitation on the materials herein employed or on the scope of our invention the following examples are provided.

EXAMPLE I Multifunctional polymerization initiators were prepared by reacting various compounds containing at least 2 carbon-carbon double bonds with the organomonolithium compound in the presence of triethylamine. Conditions employed for initiator preparation are given below.

Recipe Unsaturated compound millimoles 10 sec-Butyllithium a do (b) Triethylamine do 10 Temperature F 158 Time hours 1 n A solution of 1.15 M concentration in heptane. b Variable.

In each of the above runs, the unsaturated compound containing at least 2 carbon-carbon double bonds was charged to the-reactor first followed by triethylamine and sec-butyllithium after which each mixture was agitated at 158 F. for 1 hour. At the end of each reaction period, 50 milliliters of dry hexane was added to each mixture and the precipitate allowed to settle. The supernatent liquid was decanted from each mixture and 50 mls. of dry cyclohexane was added to each mixture. Each cyclohexane dispersion of the multilithium initiator was analyzed by titration of a known volume of the dispersion with standardized HCl using phenolphthale'in indicator to determine the endpoint. The multilithium initiators then were utilized in the polymerization of isoprene in a series of runs. The polymerization recipe and results are shown below.

8 -In each of these runs, cyclohexane was charged to the reactor first and purged with nitrogen. Tetrahydrofuran was added next followed by butadiene and then the initiator. Each mixture was agitated at 158 F. for 0.5 hour during which time the butadiene was polymerized to Reclpe completion. Styrene was added next and each mixture Cyclohexane parts by weight" 790 agitated at 158 F. for 0.5 hour. To each polymerization Isoprene do- 100 mixture, at the end of the styrene polymerization, an Inltlat I 0f mp e I, m q m- (b) antioxidant solution was added. The solution was Temperature F 158 10 weight percent of 2,2-methylene-bis(4-methyl-6-tert-bu- Time hours 20 tylphenol) in a 50/50 by volume mixture of isopropyl aMeqhm=mi1ucquiva1ents of lithium per 100 grams r alcohol/toluene. The amount of the solution added was g g i a sufficient amount to provide 1 part of the antioxidant at a T per 100 parts of polymer product. The terminated mix- ABLE H tures were each stirred with isopropyl alcohol and the pre- Initiator Percent cipitated polymers Separated and dried.

Run U tu atio d The above example demonstrates utilization of the 0 m pg multifunctional initiators of this invention in making block 0m cs copolymers or butadiene/styrene.

A 100 5.2 85 8.05 B 100 5.2 87 8.17 EXAMPLE III 0 100 5.3 86 8.29 D 100 5. s 82 7. 34 A multifunctional polymerization initiator was prepared g $3 3': 2:23 by reacting 1,3-butadiene with sec-butyllithium in the o 100 6.1 80 5.38 presence of the polar compound triethylamine. The H 100 78 initiator preparation recipe is shown below. b Determined according to procedure of U.S. Patent 3,278,508, 001. 20 i= i 1i din t 1 iU s t3 27s 50s Recipe C911- goylrlrgiesfielrege-ree accor g oproee ureo .Paten 13 butadiene minimolfl 50 ngeetegnmed according to the procedure of U.S. Patent 3,215,679, col. Triethylamine 50 30 sec-Butyllithium do 100 In each of these polymerization runs, cyclohexane was Temperature F 158 charged to the reactor first followed by a nitrogen purge. Time h ur" 1 The isoprene was added next followed by the 1n1t1ator and A solution f 1A5 M concentration in cyclohexane. the mixture agitated at 158 F. for 20 hours. At the end In th f th b t th 1 3 b t of each polymerization reaction a 10 weight percent solue gg g a n e i 5 g' tion of 2,2 methylene-bis(4-methyl-6-tert-butylphenol) was a Y met Y amule e was added to the mixture in a 50/50 by volume mixture of q 'i p' At the end 9 the reactlon pglod isopropyl alcohol/toluene, The amount of this antioxidant during Whlch the mlxture was agltated preclpltate Solution was Sufficient in amount to provide 1 part of the was allowed to settle and the supernatant l1q u1d removed. antioxidant per 100 parts of polymer. Each mixture was 40 Dry hexane. (50 was added and nilxture Shaka then stirred with isopropyl alcohol to precipitate the polyand the Sohd allowed to W and the hquld f' y as mer. The polymer from each run was separated and dried. before i hexane washmg .f repFated twice m the The above example and results Shown in Table II demon same fashlon and the solid initiator dispersed m 100 m1. strate the preparation of the multifunctional initiators of of y i i this invention and utilization of these initiators in making Thls mlilator employed senes of Polymenza' high cis l,4 polyisoprene t1on runs in which styrene/butadiene/styrene(20/60/20) block copolymers were prepared. The polymerization EXAMPLE II recipe and results are shown below. Initiators from Example I were employed in a series polymerization recipe of runs in which block copolymers of styrene/butadlene/ Styrene (20/60/20) were prepared. Polymerization recipe cyclollexane "Parts by welghtn- 790 and results are shown below. Butadlene 60 Styrene do 40 R lpe Tetrahydrofuran (THF do (a) Cyclone Parts by weight 790 Imtlator meqhm' (a) Butadiene dn T:emperature 158 Styrene 40 Time urs" 2 Tetrahydrofuran do 1.5 n v mm Initiator of Example I, meqhm. do 2.0 TABLE Iv Temperature -F 158 60 G E1 O T 1 Initiator, THF, Conv., tens ii g t i ii, Run No meqhm. phm. percent p.s.i. percent TABLE III 4. 0 1. 0 100 2, 400 1, 000 as it as 223 .323 Run No. Conv., a iii 1135? 5 g 1 3 $8 52 2 '33 Run No of Ex. I percent p.s.i. percent 5 g: g fig Egg 1 133 21 0 21 0 100 1: s00 1: 000 100 250 700 2. 5 2. 0 100 2, 300 1, 000 0 1: 020 800 3. 0 2. O 100 1, 900 1, 000

1' $8? Results detemined as desnbed m Table III of Example 11. 100 1,000 35 100 1,600 so: In each of the above runs, cyclohexane was charged to the reactor first followed by a nitrogen purge. The 1,3- butadiene was added, tetrahydrofuran and then the initiator were charged. 1,3-butadiene was polymerized to completion in 1 hour at 158F. followed by the addition of the styrene which was polymerized for 1 hour at 158 F. Each of the polymerization runs was terminated as described in Example II and the polymers recovered and dried as described in Example II.

The above results further demonstrate the utility of the multifunctional initiators of this invention and the preparation of block copolymers having high green tensile strength and elongation properties.

' EXAMPLE 1V 1,5-hexadiene, sec-butyllithium, and triethylamine, according to theirecipe of'Example I were usedin the polymerization of butadiene and styrene according to the recipe and procedures of Example II, Table III, Run 3. The components were not allowedto pre-react before use as a polymerization initiator. This run gave a 100 percent conversion of polymerbut the polymer had no measurable green tensile strength. In contrast, Run 3 of Table III of Example 11 shows avolue of 2250 for green tensile strength. These results demonstrate that a styrene/butadiene/styrene teleblock polymer was not formed when the reaction step for initiator formation of this invention was omitted. This, in turn, indicates that the multifunctional initiator was not formed when the initiator components were not allowed to react according to this invention.

EXAMPLES V-VII In theexamples shown hereinafter, various polymers or'copolymers were prepared employing general recipes as shown below:

POLYME RIZATION RECIPES Time, minutes Dimethyidiehlorosilane or con tetrachloride. Mixed chlorostyrene Extender oil a Variable Variable. sili- None or variable.- None or variable.

Do. I None or 37.5.

10 Preformed initiators prepared as described were made with varying Li:K ratios and used to prepare polybutadiene polymers using the polymerization recipe shown hereinbefore. The preformed hydrocarbon soluble initiators were easy to handle and utilize in the polymerization process. Results were obtained as follows:

a As determined by ASTM D 1646-63.

* As determined by U.S. 3,278,508, 001. 20, line 71, col. 21, line 21.

e The ratio of Weight average molecular weight to number average molecular weight as determined by gel permeation chromatography Data above show a noticeable change in Mooney viscosity and heterogeneity index of polymers formed with Li:K ratios of lower range as compared to those of higher Li:K ratios above about two. Also, it is apparent from Table V that the vinyl unsaturation tends to increase at lower ratios, cis unsaturation tends to decrease at lower ratios, while trans changes relatively slightly. These runs illustrate the versatility of these unique multifunctional initiators in preparing polymers of varying molecular weight and varying configurations as may be desired.

EXAMPLE VI Further runs were made with the multifunctional initiators in processes of polymerization of butadiene and styrene. Results obtained were based on a copolymerization recipe as shown hereinabove employing an eifective initiator level of 0.8 meqhm. lithium at a Li/K ratio of 10:1,

l Added to polymer solutions after polymerization. wi h results as f l TABLE VI FEN 11/1/ Normalized unsat- Sample 71 Bound uration, percent Heterotime, Conv., styrene, Inherent Mooney, geneity Bd/S ratio min. percent percent viscosity ML-4 Trans Vinyl inde x I Initiator formed in situ 74.4I24.B.'.-. 90 96. 9 25. 1 1. 36 18 46. 4 13. 5 1. 33

I i Initiator preformed for 1 hour Preformed 7 days The' above recipes were used in polymerizations' employing the process of myinvention or in comparative run forcontrol. purposes.

EXAMPLE v Preformed multifunctional initiators were prepared using the following recipe;

Initiator recipe Amount Cyclohexane ml. Potassium t-amyloxide (KTA) Variable. Butadiene 2.59 g.==48 mmoles. n-Butyllithium (NBL) 1O mmoles. Temperature, F. 158.

Contacting time, minutes 40.

1 Examples were taken at intervals over the course of each polymerization, conversion and extent of bound styrene determined. These data showed that rates of polymerization and of styrene incorporation showed little difference for the three initiators. These data demonstrate effectiveness of the multifunctional initiators, as well as stability over long intervals of time after preparation EXAMPLE VII time of addition of thereof which was of varying duration.

Conversion in each run was essentially quantitative.

The presence of gel in polymers treated with either terminating agent indicates the presence of multiple active lithium atoms per polymer molecule in the reaction mixture at the end of polymerization and prior to quenching.

As will be evident to those skilled in the art, various modifications of this invention can be made or followed, in light of the discussion and disclosure herein set forth, without departing from the scope and spirit thereof.

What is claimed is:

1. A process for producing multifunctional polymerization initiators which comprises contacting (I) a hydrocarbylmonolithium compound with (II) at least one compound containing at least two carbon-carbon double bonds and which is aliphatic hydrocarbon, alicyclic hydrocarbon, or tertiary heterocyclic-nitrogen-containing compounds, in the presence of (III) a polar organic compound which is alkali metal alkoxide, sec-amine, tert-amine, or hexaalkylphosphoramide wherein is employed a molar ratio of said (III) polar organic compound to said (II) compound containing at least two carbon-carbon double bonds of about 0.001 to 10:1, and which further employs a ratio of said (I) hydrocarbylmonolithium compound per each carboncarbon double bond in one mole of (II) of about 0.01 to 10.

2. The process as defined in claim 1 wherein (I) hydrocarbylmonolithium compound is represented by RLi 'wherein R contains 1 to 12 carbon atoms and is alkyl, cycloalkyl, aryl, cycloalkenyl, alkenyl, or combination thereof,

said (II) aliphatic hydrocarbon contains 3 to 30 carbon atoms per molecule and is represented by wherein each R is hydrogen, or a radical containing 1 to 27 carbon atoms and is alkyl, alkenyl, cycloalkyl, or cycloalkenyl, or combination thereof, wherein at least one said R is alkenyl or cycloalkenyl;

said alicyclic hydrocarbon contains 5 to 30 carbon atoms per molecule and is monocyclic or polycyclic conjugated or nonconjugated diene or polyene;

said tertiary nitrogen-containing heterocyclic compound contains 4 to 30 carbon atoms per molecule, from 1 to 3 tertiary nitrogen atoms per molecule, and is monocyclic or polycyclic diene or polyene;

said alicyclic hydrocarbon and said tertiary nitrogencontaining heterocyclic compound can contain exo-- cyclic carbon-carbon unsaturation;

said (III) alkali metal alkoxide contains 1 to 20 carbon atoms per molecule and the alkali metal thereof is litium, sodium, potassium, rubidium, or cesium;

said sec-amine is represented by:

12 wherein each R contains 1 to 20 carbon atoms and is alkyl, cycloalkyl, aryl, or combination thereof, and said R radicals together with the N can form a ring; said tert-amine is represented by:

R! RII I!I RII wherein each R" contains 1 to 20 carbon atoms and is alkyl, cycloalkyl, aryl, or combination thereof,

and said R" radicals together with the N can form a saturated heterocyclic ring containing 4 to 7 carbon atoms; and wherein said hexaalkylphosphoramide is represented by the general formula:

R!!! \N- =0 R! g R!!! RIII wherein each R' is an alkyl radical containing 1 to 8 carbon atoms.

3. The process according to claim 1 wherein said molar ratio of said (III) polar organic compounds to said (H) compound containing at least two carbon-carbon double bonds is about 0.5 :1 to 2:1, and wherein are employed about 0.75 to 1.25 moles of said (I) hydrocarbylmonolithium compound per each carbon-carbon double bond in one mole of said (II), and wherein said contacting is conducted for a time of about 10 seconds to 72 hours and at a temperature of about 0 to 150 F.

4. The process according to claim 1 wherein said molar ratio of said (I) hydrocarbylmonolithium compound per each carbon-carbon double bond in said (H) is less than about 0.5, said (HI) reactant is said aliphatic hydrocarbon and is a polymerizable conjugated diene, and said multifunctional initiator is substantially hydrocarbon soluble.

5. The process according to claim 1 wherein said contacting time is about 0.25 to 6 hours, and said contacting temperature is about 30 C. to C., and wherein said contacting further is performed in the presence of an inert hydrocarbon diluent containing 4 to 10 carbon atoms per molecule.

6. The process of claim 1 wherein said (11) is 1,3-butadiene; 4-vinyl-cyclohexene; 2,6-dimethyl-2,7-octadiene; 1,5-hexadiene; 2,5-dimethyl-1,S-hexadiene; 1,5-cyclooctadiene; 1,2,4-trivinylcyclohexane; linear butadiene trimer; or 2,5-dimethyl-2,4-hexadiene; said (II-I) polar compound is triethylamine; and said (I) hydrocarbylmonolithium compound is sec-butyllithium.

7. The process of claim 1 wherein said (H) is 1,3-butadiene; said (III) is potassium t-amyloxide, and said (I) is n-butyllithium.

8. The polymerization initiator prepared by the process of claim 1.

References Cited UNITED STATES PATENTS 3,301,840 1/ 1967 Zelinski 260-879 3,377,404 4/1968 Zelinski 260-665 R 3,492,369 1/ 1970 Naylor 260-879 3,644,322 2/ 1972 Farrar 26094.2 M

DANIEL, E. WYMAN, Primary Examiner A. P. DEMERS, Assistant Examiner US. Cl. X.R.

252-431 R; 260-851, 94.2 M, 94.7 A, 879

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 3,73h,972 Floyd E. Naylor et a1 Dated: y 1973 Patent Noa It is certified hat error appears in the above-identified patent. and that sa; Letters Patent are hereby corrected as shown below:

Column 12; line 35, (III) should be (II) Signed and sealed this 17th day of September 1974.

(SEAL) Attest:

McCOY M. GIBSON JR. c. MARSHI..L DANN Attesting Officer Commissioner of Patents 

